Abstract
A copper(I)-catalyzed asymmetric borylative cyclopropanation of bulky silyl-substituted allylic electrophiles for 1,2- cis -silyl-boryl-cyclopropanes has been developed. Highly strained cis -cyclopropanes were obtained in excellent yield and stereoselectivity by employing a newly developed backbone-modified three-hindered-quadrant bisphosphine ligand (up to 97% yield; 98% ee; cis / trans = >99:1; cyclopropane/allylboronate = >99:1). Detailed computational studies suggested that the highly rigid phosphine conformation of the backbone-modified ligand, which is virtually undisturbed by the steric interaction with the bulky silyl-substituted allyl electrophiles, is key to the high stereo- and product-selectivity. Furthermore, the detailed computational analysis provided insight into the mechanism of the stereo-retention or -inversion of the chiral alkylcopper(I) intermediate in the intramolecular cyclization.
Sign-in/Register to access full text options 
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Schedule a callDisclaimer: All third-party content on this website/platform is and will remain the property of their respective owners and is provided on "as is" basis without any warranties, express or implied. Use of third-party content does not indicate any affiliation, sponsorship with or endorsement by them. Any references to third-party content is to identify the corresponding services and shall be considered fair use under The CopyrightLaw.
